US8545584B2 - Glass fiber structure designed to reinforce bonded abrasive articles - Google Patents

Glass fiber structure designed to reinforce bonded abrasive articles Download PDF

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Publication number
US8545584B2
US8545584B2 US12/665,142 US66514208A US8545584B2 US 8545584 B2 US8545584 B2 US 8545584B2 US 66514208 A US66514208 A US 66514208A US 8545584 B2 US8545584 B2 US 8545584B2
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United States
Prior art keywords
novolac
wax
resin composition
weight
transition temperature
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Expired - Fee Related, expires
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US12/665,142
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English (en)
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US20100180512A1 (en
Inventor
Alix Arnaud
Philippe Espiard
Claire Ceugniet
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Saint Gobain Adfors SAS
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Saint Gobain Adfors SAS
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Assigned to SAINT-GOBAIN TECHNICAL FABRICS EUROPE reassignment SAINT-GOBAIN TECHNICAL FABRICS EUROPE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CEUGNIET, CLAIRE, ARNAUD, ALIX, ESPIARD, PHILIPPE
Publication of US20100180512A1 publication Critical patent/US20100180512A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/34Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06Waxes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2964Artificial fiber or filament
    • Y10T428/2967Synthetic resin or polymer

Definitions

  • the present invention relates to the field of abrasives. It relates more precisely to a structure based on glass fiber coated with a resin composition designed to reinforce bonded abrasive articles, in particular grinding wheels, the resin composition used for coating this structure and the bonded abrasive articles incorporating such a structure.
  • Abrasive articles contain a multitude of abrasive particles solidly bound together by a binder. These articles are widely employed for machining parts made of various materials, particularly in cut-off, deburring, surface grinding and polishing operations.
  • Bonded abrasive articles to which the invention more particularly relates are abrasive grinding wheels for cutting of hard materials, in particular steel. These grinding wheels are employed on machines operating at a high peripheral speed, and on account of this must be able to withstand high mechanical stresses produced by the latter.
  • abrasive grinding wheel it is usual to consolidate the abrasive grinding wheel by incorporating therein at least one structure based on reinforcing yarns, particularly glass fiber yarns that may be for example in the form of a fabric.
  • the reinforcing structure is obtained by passing the glass fiber through a bath with a resin composition consisting of an alcoholic solution containing of the order of 70% by weight of resin, and then passing it between two rollers so as to remove the excess resin, and finally in a chamber heated to a temperature of the order of 100 to 145° C. for a maximum of a few minutes so as to reduce the quantity of solvent based on the resin to a value of approximately 5% to 10%.
  • the reinforcing structure obtained in this way is collected in the form of a winding, for example a reel, or is cut up either into sheets or directly into the desired shape and dimensions of the final grinding wheel, for example by means of a punch.
  • the abrasive grinding wheel is obtained according to the method that consists of placing in a mold, alternately, several layers of the mixture of abrasive particles and binder on the one hand, and of the reinforcing structure on the other hand, and of molding the assembly by compression either hot or cold.
  • the article obtained is treated thermally under temperature conditions enabling the binder to be crosslinked and finally to obtain the abrasive grinding wheel.
  • thermosetting resin chosen from:
  • the aforementioned resin compositions are not costly and they enable reinforcing structures to be obtained that exhibit good properties, particularly in terms of flexibility and adhesive power.
  • the structure has a sufficient high flexibility, that is to say the resin is not too “hard” so that the cutting operations as previously described can be carried out under acceptable conditions, by generating the least possible dust and by operating so that the resin is not removed in the vicinity of the cut edges of the structure (glass is not laid bare).
  • the adhesive power also called “tack”
  • the adhesive power also called “tack”
  • non-polluting resin compositions available, that is to say those that contain—but also that generate during application to the reinforcement structure or subsequently—the fewest possible compounds considered as being able to harm human health or the environment.
  • Urea-formaldehyde resins are not heat-stable and degrade while liberating formaldehyde as soon as the temperature exceeds 100° C. Formaldehyde may thus be released when the reinforcing structure is produced, during drying in the heated chamber and when the abrasive grinding wheel is used.
  • Phenolic resins are obtained by the condensation of phenol and formaldehyde, either in a formaldehyde/phenol molar ratio less than 1 in the presence of an acid catalyst (novolacs) or in a formaldehyde-phenol molar ratio greater than 1 in the presence of a basic catalyst (resols).
  • Novolacs contain virtually no free formaldehyde but they are used in conjunction with a crosslinking catalyst such as hexamethylenediamine and hexamethylenetetramine that is not heat-stable and generates emissions of formaldehyde and ammonia during the production of the reinforcing structure and use of the abrasive grinding wheel.
  • Resols contain free formaldehyde in a relatively high quantity.
  • the object of the present invention is to develop a resin composition capable of coating a glass fiber structure designed to reinforce bonded abrasive articles, and in particular grinding wheels, that gives the structure great flexibility and low adhesive power, and that limits the risk of polluting emission of formaldehyde and nitrogen-containing compounds.
  • novolacs having different glass transition temperatures and wax has proved to be particularly valuable for producing a resin composition capable of coating a glass fiber structure that is suitable for the reinforcement of bonded abrasives.
  • the properties of the novolacs and wax are in point of fact complementary.
  • the novolac having the lower glass transition temperature gives flexibility to the structure and makes it possible to have a high level of flexibility. It makes it possible to compensate for the too high rigidity of the novolac with a higher glass transition temperature and in this way to adjust the flexibility to the desired level.
  • the novolac having the lower glass transition temperature that is to say below or equal to 60° C., represents 50 to 80% by weight of the mixture of novolacs.
  • the glass transition temperature of the novolac with the lower glass transition temperature is above 40° C.
  • the glass transition temperature of the novolac having the higher glass transition temperature is above or equal to 80° C., and advantageously lower than or equal to 100° C.
  • Novolacs according to the invention may be chosen from novolacs known to a person skilled in the art obtained by reacting a phenolic compound, preferably phenol, and an aldehyde, preferably formaldehyde, in the presence of an acid catalyst (pH of the order of 4 to 7).
  • an acid catalyst pH of the order of 4 to 7
  • the formaldehyde/phenol molar ratio varies from 0.75 to 0.85.
  • the choice of novolac is made according to the desired glass transition temperature.
  • Novolacs that may be used within the context of the invention contain less than 0.1% by weight of free formaldehyde, and preferably less than 0.05%.
  • Wax acts as an “antiblocking” agent and makes it possible to compensate for the high adhesive power of the novolac that has the lower glass transition temperature.
  • an adhesive power that is not too high makes it possible, on the one hand, to preserve cut reinforcing structures in a very valuable state of cleanliness that avoids contamination by dust, and on the other hand makes it possible to handle these cut structures with a minimum risk of their adhering to each other under moderate pressure, notably during storage.
  • the wax is chosen from paraffin waxes, for example polyethylene or polypropylene waxes, and ethylenebisamide waxes, notably N,N′-ethylenebis(steramide).
  • the wax is microcrystalline.
  • the wax content does not exceed 5% by weight of solid matter of the resin composition, and advantageously is less than or equal to 3%.
  • the plasticizing agent contributes to an improvement to the flexibility of the resin composition.
  • examples of such agents mention may be made of alkylphosphates, phthalates, triethanolamine, oils and polyhydric alcohols, notably glycerol and glycols.
  • the plasticizing agent content does not exceed 1% by weight of solid matter of the resin composition.
  • the resin composition coating the reinforcing structure according to the invention does not contain any crosslinking agent, which is particularly advantageous since novolacs may preserve their initial thermoplastic nature.
  • the resin composition is not likely to change with time so that the reinforcing structure may be stored for a very long period, which is a supplementary advantage compared with known resin compositions.
  • the reinforcing structure may be composed of continuous glass yarns, preferably in the form of a nonwoven such as a web or a mat, a mesh or fabric, or of a mat of cut strands.
  • the glass yarns are yarns called “reinforcing”, produced industrially from molten glass threads flowing from the multiple orifices of a die, these threads being drawn out mechanically in the form of continuous filaments that are assembled into a base yarn and then collected by reeling on a rotating support.
  • the glass yarns according to the invention are thus base yarns, and products derived from these yarns, in particular assemblies of these base yarns in laminates. Such assemblies are obtained by simultaneously unreeling several coils of base yarns and then assembling them into meshes that are reeled onto a rotating support.
  • the glass yarns may undergo a twisting operation in order to produce textile yarns for producing fabrics.
  • the glass yarns consist of glass filaments of which the diameter may vary widely, for example from 9 to 24 ⁇ m, preferably 9 to 17 ⁇ m.
  • the glass yarns have a count (or linear mass) of between 34 and 4800 tex, preferably between 34 and 1200 tex.
  • the yarns may consist of any type of glass, in particular E, C and AR (alkali-resistant). Preferably, they consist of E glass.
  • the structure is a fabric composed of glass yarns, having a grammage that varies from 100 to 1000 g/m 2 .
  • the resin composition itself, before it is applied to the reinforcing structure, also constitutes an object of the invention.
  • the resin composition comprises the following compounds, expressed in percentage by weight:
  • alcohol As an alcohol according to the invention, mention may be made of methanol, ethanol, isopropanol and mixtures of these alcohols.
  • the resin composition may be prepared by simply mixing the constituents in a suitable vessel, advantageously provided with stirring means.
  • the novolacs are preferably in the form of a solution, in ethanol or a mixture of ethanol and methanol, the wax is a dispersion in water and the plasticizing agent is liquid.
  • the resin composition may contain additives such as emulsifiers, pigments, fillers, antimigration agents, coalescing agents, wetting agents, biocides, organosilanes, antifoam agents, colorants and anti-oxidant agents.
  • additives content does not exceed 3% of solid matter of the resin composition.
  • the coated reinforcing structure is carried out continuously by passing it first of all through an impregnating bath consisting of the liquid resin composition, and then through the nip of a calendering device composed of two rollers, which makes it possible to adjust the resin composition content to a value close to 30% by weight of solid matter, and finally through a heated chamber so as to remove part of the solvent.
  • the chamber comprises a first zone heated to a temperature of the order of 130° C. and at least one second zone heated to a temperature of the order of 110° C., the dwell time of the reinforcing structure in both zones being generally less than ten minutes, preferably varying from 30 seconds to 3 minutes.
  • the percentage solvent in the reinforcing structure is less than 12% and advantageously less than 10%.
  • the reinforcing structure obtained is then collected in the form of a reel and cut up either into sheets or directly in the shape and dimensions of the final abrasive grinding wheel, these cut structures being then stored in the form of stacks.
  • the reinforcing structure according to the invention may be used in particular for producing bonded abrasive articles such as abrasive grinding wheels, these articles thus constituting an object of the invention.
  • abrasive articles may be produced in particular according to compression molding techniques known to a person skilled in the art.
  • the abrasive grinding wheels may be obtained by depositing several alternate layers of a granular mixture of abrasive particles inside a mold, and the reinforcing structure previously cut up to the dimensions of the mold.
  • the number of reinforcing structures varies according to the desired level of the performance for the abrasive grinding wheel; generally, this number does not exceed 10.
  • the mold is put under pressure sufficient to form a “green” part that exhibits cohesion so that it may be handled and processed in the following steps without substantial modification to the shape and dimensions.
  • the mold may be heated during compression (hot molding) to a temperature that is generally below 170° C. or even 150° C.
  • the binder at this stage is in the non-crosslinked state.
  • the green part is removed from the mold and heated in an oven at a temperature enabling the binder to crosslink and to give a hardened polymer network that gives the part its final form.
  • Crosslinking is carried out according to a conventional curing cycle that consists of bringing the green part to a temperature of the order of 100° C. and of holding it at this temperature for 30 minutes to several hours so that the volatile products formed may be removed.
  • the part is then heated to a temperature of the order of 200 to 250° C. for 10 to 35 hours.
  • the abrasive grinding wheel obtained in this way may be used in all types of application that require abrasive properties, for example sanding, deburring, surface finishing operations, and more particularly the cutting of hard materials, such as steel.
  • a resin composition was prepared comprising the following constituents:
  • the resin composition had the following properties:
  • a resin composition was prepared comprising the following constituents:
  • the resin composition had the following properties:
  • a resin composition was prepared under the conditions of example 1, modified in that it only contained the novolac (1) :
  • the resin composition had the following properties:
  • a resin composition was prepared under the conditions of example 1, modified in that it comprised the following constituents:
  • the resin composition had the following properties:
  • a resin composition was prepared under the conditions of example 1, modified in that it comprised the following constituents:
  • the resin composition had the following properties:
  • This example illustrates the application of the resin composition in a semi-industrial installation.
  • a glass fiber fabric (grammage): 198 g/m 2 ; warp thread: EC 204 tex s/z; weft thread RO 408 tex), 0.5 m wide, unwound from a reel, was disposed on a coating line operating continuously. On its path, the fabric passed into an impregnating bath containing the resin composition and was then treated in an oven comprising a first section heated to 125° C., and a second section heated to 115° C., before being collected in the form of a reel.
  • the resin composition comprised the following constituents:
  • the reinforcing fabric had the following properties:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Ropes Or Cables (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
US12/665,142 2007-06-18 2008-06-18 Glass fiber structure designed to reinforce bonded abrasive articles Expired - Fee Related US8545584B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0755818 2007-06-18
FR0755818A FR2917403B1 (fr) 2007-06-18 2007-06-18 Structure de fils de verre destinee a renforcer des articles abrasifs agglomeres
PCT/FR2008/051088 WO2009004250A2 (fr) 2007-06-18 2008-06-18 Structure de fils de verre destinee a renforcer des articles abrasifs agglomeres

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2008/051088 A-371-Of-International WO2009004250A2 (fr) 2007-06-18 2008-06-18 Structure de fils de verre destinee a renforcer des articles abrasifs agglomeres

Related Child Applications (1)

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US13/939,271 Division US9556356B2 (en) 2007-06-18 2013-07-11 Glass fiber structure designed to reinforce bonded abrasive articles

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US20100180512A1 US20100180512A1 (en) 2010-07-22
US8545584B2 true US8545584B2 (en) 2013-10-01

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US13/939,271 Expired - Fee Related US9556356B2 (en) 2007-06-18 2013-07-11 Glass fiber structure designed to reinforce bonded abrasive articles

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US (2) US8545584B2 (fr)
EP (1) EP2162406B1 (fr)
JP (1) JP5411132B2 (fr)
CN (1) CN101687699B (fr)
AT (1) ATE534613T1 (fr)
AU (1) AU2008270043B2 (fr)
BR (1) BRPI0813468A2 (fr)
ES (1) ES2377679T3 (fr)
FR (1) FR2917403B1 (fr)
PL (1) PL2162406T3 (fr)
RU (1) RU2466853C2 (fr)
UA (1) UA99135C2 (fr)
WO (1) WO2009004250A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130111822A1 (en) * 2010-04-21 2013-05-09 Saint-Gobain Adfors Glass strand structure designed to reinforce bonded abrasive articles

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CN102107398B (zh) * 2009-12-29 2014-07-16 圣戈本磨料股份有限公司 高研磨性能的涂覆的磨料
US9782872B2 (en) 2012-04-26 2017-10-10 Saint-Gobain Abrasives, Inc. Tool
WO2014210426A1 (fr) * 2013-06-28 2014-12-31 Saint-Gobain Abrasives, Inc. Article abrasif renforcé par des fibres discontinues
US9855639B2 (en) * 2013-06-28 2018-01-02 Saint-Gobain Abrasives, Inc. Abrasive article
CN104249309A (zh) 2013-06-28 2014-12-31 圣戈班磨料磨具有限公司 用不连续纤维强化薄轮
CN103752594B (zh) * 2013-12-27 2016-05-25 暨南大学 一种邻苯二甲酸酯污染土壤的植物修复方法
CN109415552B (zh) 2016-07-08 2022-08-05 马萨诸塞大学 增塑的热固性树脂及相关的固化树脂、固化方法及包含固化树脂的制品
CN109415553B (zh) 2016-07-08 2022-08-05 马萨诸塞大学 增塑的热固性树脂及相关固化树脂、固化方法和包含固化树脂的制品
CN114752179B (zh) * 2022-06-02 2023-07-07 泰山玻璃纤维有限公司 低浮纤的聚甲醛组合物及其制备方法

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WO2009004250A3 (fr) 2009-03-05
FR2917403B1 (fr) 2009-07-31
US20100180512A1 (en) 2010-07-22
FR2917403A1 (fr) 2008-12-19
US20130338288A1 (en) 2013-12-19
CN101687699B (zh) 2013-01-02
CN101687699A (zh) 2010-03-31
EP2162406A2 (fr) 2010-03-17
UA99135C2 (ru) 2012-07-25
BRPI0813468A2 (pt) 2015-02-03
RU2466853C2 (ru) 2012-11-20
AU2008270043A1 (en) 2009-01-08
ATE534613T1 (de) 2011-12-15
JP2010530811A (ja) 2010-09-16
AU2008270043B2 (en) 2015-02-05
US9556356B2 (en) 2017-01-31
ES2377679T3 (es) 2012-03-29
EP2162406B1 (fr) 2011-11-23
RU2010101202A (ru) 2011-07-27
JP5411132B2 (ja) 2014-02-12
PL2162406T3 (pl) 2012-05-31
WO2009004250A2 (fr) 2009-01-08

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